Colored reflex light reflector



Aug.' 28, 1945. P. 4v. PALMQUlsT 2,383,884

COLORED REFLEX LIGHT REFLECTOR Filed June 12, 1944 ffy-f INVENTOR.

Patented Aug. 28, 1945 2,383,884 COLORED REFLEX LIGHT REFLECTOR New Canada Township,

Philip V. Palmquist,

Ramsey County,

Minn., assignor to Minnesota & Manufacturing Company, St. Paul,

Minn.,

a corporation o! Delaware Application June 12, 1944, Serial No. 539,918

(ci. s's-sz) 11 Claims.

This invention relates to colored reflex light reflector sheets and signs wherein a light-returning layer of contiguous small transparent spheres (beads) overlies and is spaced from a metallic reflecting surface having a specular or semispecular silvery characteristic. The transparent spheres are uncolored, such as are made from clear transparent glass. Between the spheres and the'underlying reflector surface there is an interposed layer or stratum of a transparent film material which is colored so as to constitutea colored light filter, and which may also serve as a spacer to hold the spheres in the desired spaced position. This transparent color layer eliminates the silvery appearance and produces the desired colored appearance, such as red, yellow, green, etc. This color layer may be formed by multi-color printing so as to provide the insignia of a sign.

This application is a continuation-impart of my copending applications Ser. No. 351,168, filed August 3, 1940, and Ser. No. 518,846, filed January 19, 1944 (since issued as Patents Nos. 2,354,048 and 2,354,049, respectively, on July 18, 1944).

An incident beam or ray of light striking the reflex reflector is refracted by the spheres,` and reflected by the underlying reflecting surface, in such manner that a. brilliant cone of light is selectively returned toward the source, even though the incident light strikes at an angle (see Fig. 6). Road signs and markers of this reflex type have greater visibility at night than do ordinary signs, to the occupants of approaching vehicles, because less of the reflected light is dissipated outside lthe field of viewing; the reflected light being concentrated in a narrow cone which is substantially coaxial with the incident beam of light coming from the headlights of the vehicle, and hence the occupants of the vehicle are located within the cone of intense reflected light.

This reflex reflecting characteristic, which is so important for night viewing, does not interfere with the daytime visibility of the sign when viewed by diffused sunlight. A more detailed discussion of the general optical principles has been given in my Patent No. 2,294,930 (issued September 8, 1942).

The present invention relates particularly to -providing reflex reflector sheets and signs which have a colored appearance. Coloration of the glass bead type of reflex reflector has been obtained in the past by using colored spheres. This expedient has numerous disadvantages, includthe variety of desired colors, to provide colored transparent glass beads which will not change color when exposed outdoors to the elements and the rays of the sun; and it is necessary to maintain stocks of differently colored beads in order to be prepared to make up sheets or signs of different colors. If two or more areas of different color are to be provided on a single reflective base sheet, it is necessary to apply the beads of different color in separate operations. Another expedient is to apply a transparent colored coating over the layer of beads, but if this is made thick enough to provide adequate intensity of.

color it will interfere with the desired refractive action of the beads, and in addition the exposure of sucn a coating to tne elements and the suns rays may result 1n deterioration. Another expedlent 1s to employ an underlying pigmented reflector, the use of 4colored pigment providing the color effect. This results in a substantial loss of light intensity due to the absorptive and diffusing nature of' colored pigment reflective surfaces, and the color effect is quite dif'- ferent from that produced by the present invention.

The present invention provides colored reflex reflection by employing an underlying silvery metallic reflector surface in combination with an interposed colored transparent layer or stratum, located between the layer of uncolored transparent beads and said silvery reflector surface. The reflector surface may be provided, for example,

by a metal lm such as a plating of silver, aluminum or tin, or a foil or' aluminum or tin; or by a stiff metal sheet having a polished reflective surface such as a sheet of aluminum, stainless steel or chromium plated metal; or by a coating containing aluminum flake pigment which lies approximately flat at the surface. Such a reflector surface has a specular (mirror) or semispecular reflectance characteristic, which makes for very brilliant or intense reflex reflection. A

silvery appearance would be produced, and a noticeable glare, if the interposed transparent layer were uncolored. The use of an interposed transparent .color layer eliminates thesilvery appearance and reduces any glare effect, and results in an unusual color effect. There is the further feature that the interposed transparent color layer, especially as to the portions directly underlying the individual beads, is protected from the action of outdoor elements by the overlying layer of beads. A wide variety of different color lng the diiliculty of obtaining colored glass in effects can be readily produced.

'rnearecepoaucedmramby oftheprent'invcntimtunumalas have a brilliant coloration which attaitlon. Thecolorliasamvequaliwandthe eilectisaostrikmgandunasualthatithasto beseeninordertobe 58mm thiswayarevisihieatgreat These .-f...,attliesacrilioeofday disinceorcleuphcreisthefeaturethatthe colored areas smear continuous andrsohd, as thoughabrlliiantpainthadbeened. 'll'hisis duetotheractthatreiradonisbya layerotsmallsphemthebcingatleastseveral hundredpersquareindrwiththenumbermhstantiaiiylomwhenspliercsofls thanlomilsaareanployciso thatthehumaneyecannntresolvetheraysfrom individualspheresevenatclosexangesndalso arelativelyilatorsnooihsmfaceismodnced. Hweverthesesmallinwim the silvery underlying reflector surface and the tonsarethcnefm'einanentirelydilllervent` categoryandinnosuiaeemivalmttosignsmad inaccordancewiththepreoentinvmtimi.

Coloredrcexreilcctorsheei'sandgnsofthe presenttypemaybemadeupinavxrieiyofwavs, aswillhereinafterhe Sisnsmaybe made upinwhiehthecoioredareas (suchaslctpamtingorprinting oran-cen cna singlemliectivebasausingiranslnrmtcolored coaiingsnflowed by applying a transparent beadedlayerthereoverinanyofsevemlposihle ways.

Coloredreliexxefiectorsheetmaterhlmaybe manufacturedinwcbfashinninany reasonabiewidthandlmethandmsybesuppued 70 tosignmakersinrdlfomtobecuttodesired sh'apesandappiiedtodesixedbascsinmakingup signs. Sheetsofdilferuitcolorsmaybeuscdto provideareasofdiiferentcolors. Such ters,symboisand)a1efonnedby :,saassc Y sothatitcanbereadilyconformedtoirregular s1irfaces,asforexample tothesurface of anembossedmetalsgnbase. 'I'hereectorsheet may be fastened to desired base surfaces in various ways. Thus it may be tacked, stapied or riveted, or may be bonded by an adhesive or cement. It may be provided with an initial integral adhesive ooatingonthebacksoastobeinready-to-lay form.

Waterproof and weatherproof sheets and signs can be made which are highly suited to outdoor use, remaining effective for at least a year of continuous outdoor exposure to sunlight, rain, snow and extrem of temperature.

Various objects and features of the invention will additionally be apparent from the following description of illustraiive embodiments.

Inthe accompamringdrawing: Hgs.I,2,3and4areschematicdiagramsindi catinginashionthestructuresof illustrative colored reilex light reflector sheets andsisnsmadeinaccordance withthisinvention; 4

Fig. 5 is a plan view of a highway "stop sign" having (raised) lettering, over the whole surface'of which a stretchy colored reflex light-reflector sheet has been applied to provide Yimproved night visibility,- the beaded surface of thesheetbeingcoveredwithblackinkorpaintin the raised letter areas to provide black lettering asinanordinarysign'andtheremainingareas providing a contrasting colored background (such as yellow or red) both by day and by night toattractattentiontothesignandtomakethe lettering standout more plainly; and

Hg. 6 is a tic sectional view taken through one of the raised letter portions of Fig. 5, and the right hand portion illustrates the concentrated cone of reilex reflected colored light returning toward the source of an angular-1y incident ray or beam of light. a

Referringtolg. l, thereisshown adiagram illustrating in highly magnified fashion the sectional structure of a type of the product. The diagram is not a literal section view, since the spheres are spaced farther apart than is customary; and each circle represents a full circumference, which would not be the case in o, true section as the spheres are not actually arranged in rows but are packed so that a section plane could not be passed through the centers of a series of adjacent spheres. This colored reflex light reflector sh'eet or sign structure has a reflective base or sheet I0 having a silvery metallic reflective surface characterized by a specular or semi-specular reflectance characteristic. The diagram broadly applies no matter what the particular reflector may be. Thus the reflector surface may be provided by a metal sheet having a silvery reflective surface such as a. sh'eet o! aluminum, stainls steel or chromium plated metal; by a foil of aluminum or tin (which may or may not be laminated to a support); by a plating of silver, tin or aluminum; or by a flexible sheet (such as waterproofed paper) or a rigid base (such as metal or wood) coated with an aluminum paint containing aluminum flakes which lie approximately fiat at the surface. The silvery specular or semi-specular reflective nature of the surface is of great importance, and is to be distinguished from ordinary reflective painted surfaces or coatings which have a non-specular or diffusing reflectance characteristic and which are either colored or white. The reflectance reflector sheeting may be made with 75 characteristic employed in the present product is one of the essential factors in producing the desired result.

overlying and bonded to said silvery reflective surface is the colored transparent spacing lm Il, which may either be a laminated precast film or may be a film which is cast or formed in situ as a coating. The coloration of the film may be produced by use of a dye, or by inclusion of a transparentcolored pigment having substantially the same refractive index as the fllm material so as to avoid appreciable scattering of light rays passing through the film. This colored transparent film acts as a light filter and also serves as a spacing film. A transparent binder coating I2' overlies and is bonded to the colored spacing film. This binder coating may also be col-,- ored, but it is generally preferable to employ a clear, uncolored coating. When the binder coating is colored, it may have a different color than the color of the spacing film, in order to produce a day appearance which is different than the night appearance, and to cause a change in the color appearance at night as the sign is approached owingto the change` in the angle of incidence of the lightffiom the head lamps of the vehicle. It will be understood that the invention is not limited to use of' transparent binder coatings. An opaque binder coating (black, white-or colored) can be used, provided that the inner extremities of the spheres are not covered over and are in optical communication with the underlying spacing film. A lightreturning layer of small transparent spheres I3, which are clear and uncolored, is partially em,- bedded in the binder coating so as to provide a multiplicity of contiguous convex lens elements, the inner extremities touching or closely approaching the outer surface of the underlying colored spacing film and being in 4optical communication therewith. The binder coating holds theI spheres firmly in place.

The transparent spheres may be made of any suitably hard, clear, transparent solid material, such as quartz, ordinary inorganic glass, or a suitable so-called organic glass `(such as a hard polymer of methyl methacrylate). Small spheres are employed to provide several hundred, at least, per square inch. It is preferred to use spheres having an average diameternot exceeding about mils; and excellent results are obtained with spheres having an average diameter in the range of about 3 to 6 mils, in which case there will be upwards of 10,000 per square inch; thus providing a relatively smooth surface which can be readily printed or painted, if desired, and which appears continuous. The use of small spheres makes possible the production of reflex reflector sheets which are thin and pliant, and aids in making stretchy sheets. In a batch of small spheres, even after screen grading, .there will be some variation in size as between individual spheres, which preferably should be held aseass-i bending and will strike the underlying reflector I0. The reector will then emit a divergent cone of light rays which will pass out through the sphere, and upon emerging will be retracted so as to reduce the angle which the rays make with the optic axis, and will return toward the original source of light as a concentrated cone. I'he returned light is colored de to the differential color filtering action of the colored transparent spacing film. The Adegree of divergency of the rays returning toward the source from the outer sphere surface is dependent on the nature of the reflector, the refractive index of the sphere, and the thickness of the spacing film. Optimum brilliancy of reflex reflection, as viewed by an observer located near the axis of the incident light beam, is secured by an optical structure which reduces to a minimum the degree of divergency of the returning rays, so as to minimize wasting light outside the viewing zone. This is accomplished by having the incident rays strike the reflector surface when most nearly in focus and by employing a specular'or semi-specular reflective surface. A perfect focus is impossible due to the optical spherical aberration effect, even if the sphere were perfectly round, but a spacing distance can be chosen to secure the optimum of possible brilliancy. In the case of a sphere of ordinary glass, having a refractive index of about 1.50-1.55, the optimum distance [for spacing the inner extremity from the reflector, is about onethird the diameter of the sphere. The optimum spacing distance decreases with increase of refractive index of the sphere until it becomes zero (no spacing) at an index of approximately 1.85- 1.90. Over-spacing not only cause-s a loss of brilliancy but a poorer angularity characteristic. Under-spacing causes a loss of brilliancy as regards an observer close to the axis of incident light which strikes the reflector at a small angle to the normal, but produces greater angularity and divergency and hence may be desirable when an increase in these characteristics is desired.

When a layer of spheres is spaced from the refiector surface by a transparent spacing layer of uniform thickness, so that the inner extremities of the spheres are an equal absolute distance from the reflector, and the spheres diffei from each other in diameter, the spacing ratio will differ as between spheres of differing diameter. The average spacing ratio in such case may be computed by dividing the spacing layer thickness by the average diameter of the sphere. Same individual spheres will then be spaced a greater distance than others, having reference to the ratio value; those of larger than average diameter being under-spaced and those of smaller diameter being over-spaced. Hence an average spacing ratio is preferable which is slightly less than the value which would be used if all the )spheres had the same diameter, so as to insure within limits so that most of the spheres will not vary from the average diameter by more than 50%.

An incident beam of paraxial light rays (illustrated by (a) in Fig. 1) will be refracted in passing into a sphere and will converge, coming to approximate focus behind the sphere when it is of glass having an ordinary index of refraction. Assuming that substantially no refraction occurs at the rear surface of the sphere, as is true when the refractive indices of the spheres, binder coating, and spacing film are substantially the same, the convergent rays will pass through and that fewer individual spheres are over-spaced (under-spacing being preferable to over-spacing). However, useful results can be obtained even though there is a departure from' the optimum or most desirable value. In the case of ordinary glass spheres (refractive index about 1.50-1.55), a spacing distance within the range of about 2040% of the average diameter gives best results for most purposes. In commercial manufacturing practice, the optical consequences of variations in spacing can be readily observed so as to provide a guide to making adjustments to secure the desired result.

beyond the sphere Without substantial further` When the transparent spacing illm located between the spheres and the reflective surface has a refractive index substantially different than that of the spheres, the optimum spacing a distance will be different on that account, owing the same effect whatever the sphere diameter,

and hence the need of spacing to secure optimum brilliancy is not overcome by using small spheres, although the absolute distance is reduced proportionally with a reduction in sphere diameter, but have the same critical effect.

This light-returning phenomenon occurs even when the beam or rays is incident at an angle, whence the designation reiiexJ The reason is that some of the rays emitted from the reflector Ill will be within the field of the angular convergent cone which strikes it and will return toward the source along the same path, or close to it, that was followed by the incident rays. A highly specular reflector (such as a plating or highly polished foil) underlying the beads would emit few rays in the right direction to be returned to the source, when theA incident light approaches at a substantial angle, vand hence would cause poor angularity, but will producel extremely high brilllancy when the angle of incidence is relatively small. A semi-specular reflector, such as is obtained by using metallic reflecting aluminum pigment flakes which lie approximately parallel to the plane of the reflector, gives a useful combination of high brilliancy coupled with a good enough angularity such that the actual observed brilliancy is substantially greater than for non-specular reflectors up to fairly large angles (about 30). These factors, including the regulation of the spacing distance, allow of considerable lscope in design so as to obtain a reflex reflector best suited to a particular requirement.

ture wherein the total transparent stratum between the layer o1' spheres and the reflector surface is comprised of a transparent uncolored lm beneath the spheres and an underlying thin colored transparent printing coating located over the reflector surface. Y

The base or sheet I5 has a silvery metallic reective surface of the specular or semi-specular type (such as any of the kinds previously mentioned in connection with the reflector base or sheet I0 of Fig. 1); Overlying and bonded to said reflective surface is a thin transparent printing coating I6, and overlying and bonded thereto is an uncolored transparent spacing lm II. This in turn is covered by an uncolored transparent binder coating I8 in which a layer of small uncolored transparent spheres I9 is partially embedded, the inner extremities of the spheres touching or closely approaching the outer surface of the spacing lm.

The thickness of the printing coating is ordinarily much smaller than the thickness of the overlying uncolored transparent spacing film, so that the latter has substantially the same thickness as the colored spacing lm of the Fig. 1 construction and hence has approximately the same mechanical strength The colored transparent printing coating may have the same color` over the whole area; or it may have different colors in different areas so as to provide desired sign indicia (such as letters, designs, backgrounds, etc.) which is indicated in Fig. 2 by the left and right hand parts of 4printing I6, illustrating the juncture of printing areas of different color.

The ultimate product can be made upby various methods. Thus the reflective base or sheet I5 can be printed prior to application of the 4l overlyingtransparent spacing film I'I. Multi- For reflex reflector sheets to be used in making v vertical highway signs located beside the highway and at approximately right angles to it, maximum distance visibility at night by reflex reflection is obtained by using a spacing distance which gives, maximum brilliancy for small angles of incidenceI as viewed by an observer located close to the axis of incident light, and this spacing distance is in the range of approximately 20-40% of the average sphere diameter when spheres are used having a refractive index of approximately 1.50-1.55.

ThefFig. 1 structure, as shown and above described, involves a binder coating distinct from the spacing nlm. The same type of optical structure can be secured by employing a single transparent colored binder coating of suilicient total thickness to serve both functions. Control of spacing of the spheres away from the reiiector surface is then somewhat more dilllcult, but can be accomplished by using a binder coating composition of such viscosity and surface tension that the small spheres, when sprinkled thereover, will sink in to the desired extent and no more, followed by setting-up the binder to its ilnalstate.

color sign sheeting can readily be made by printing the reective sheet on a multi-color offset press. Signs can also be made by painting the reiiective base, or by using screen process methods, employing suitable transparent colored inks or paints. The colored transparent printing can then be coated with an uncolored transparent coating composition adapted to provide the transparent spacing film II, followed by appiying the binder coating and layer of spheres. Another expedient is to separately manufacture a transparent uncolored beaded sheet comprised of a transparent nlm I1, coated with a transparent binder coating I8, in which the layer of spheres I9 is embedded. This preformed beaded sheet can be laminated to the printed Surface to form the desired reflex light reflecting sign. This procedure has the advantage that the uncolored beaded sheeting can be made up and used as a single stock material for making up various signs. A further expedient is to take the uncolored transparent beaded sheeting just described and print on the dat back face thereof to provide the colored transparent printing, afterwards laminating the printed sheet to a base or sheet having a silvery metallic reective surface (such as, for example, an aluminum foil). In all of these cases the ultimate product has the same essential structure shown in Fig. 2. By using a thermo-adhesive spacing film, or thermo-adhesive printing composition, or both, direct lamination can be obtained by hot-pressing. When an interposed laminating adhesive is fused this should be transparent and relatively thin, and its thickness will constitute part of the total spacing thickness between the inner extremities of the spheres and the reflective surface.

Fig. 3 shows a colored self-sustaining flexible beaded reflex reflector sheet of what I term the backless type; in contradistinction to beaded sheet material built up on a base or backing underlying the reflector means and relied on as a support for the reflex reflecting structure and constituting an integral or permanent; element of the manufactured sheet product, remaining a part of the sheet in its ultimate location and use. The term backless does not, however, exclude the provision of a temporary support or liner to which. the inherently self-sustaining reflector sheet removably adheres, and from which it can be readily stripped, as when it is to be applied -to a desired sign base in making up a sign; nor

does it' exclude an adhesive layer or coating on the back face so as to provide a ready-to-lay sheet which can be readily adhered or bonded to `base surfaces in making up signs. This reflector sheet may be made with suflicien't stretchiness so that it can be readily conformed to irregular surfaces, as for example to the surface of an embossed metal sign base, a stretch of at least about 20% being desirable for such uses.

'I'his backless type of colored reflector sheet has a back light reflector film 2| (comprised of a binder pigmented with aluminum flakes to provide the desired silvery metallic reflection) which is flexible and, instead of being mounted on a permanent backing, serves itself as the back element of the reflector sheet structure proper. This reflector film provides a semi-specular sil-- very reflective surface. Overlying and Ibonded to said reflector film is a flexible transparent colored spacing fllm 22, which is covered in turn by a transparent binder coating 23 in which a layer of small transparent spheres 24 is partially embedded; this part of the structure thus being the same as that described in connection with Fig. 1 and details need not be repeated.

The foregoing backless reflector sheet is shown mounted on an underlying removable carrier sheet 25, which is employed as a casting web in making the backless reflector sheet, and which may be left in place as a temporary liner. This carrier sheet adheres poorly and can readily be stripped ofi when desired. In order to facilitate such removal, the back face of the reflector film may be provided with a thin back size coating 26 of such nature that the carrier sheet adheres poorly. This expedient is desirable in cases where the nature of the reflector film is such that it would adhere ltoo strongly to the surface of the particular carrier sheet employed. The back size coating may also be used to advantage when it is desired to provide a protective covering for the back face of the reflector film. Although it is an integral and permanent element and underlies the reflector film, it is not a backing in any ordinary sense and is not used to perform the function of a backing, being a mere sizing on a sheet which is itself fully .self-sustaining in the absence of such a coating.

The reflector sheet can be built up by employing a carrier sheet 25 having a smooth surface, such as a non-fibrous film (illustrated by a cellulose acetate film) or a paper sheet lwhich has been coated with a film-forming composition which results in a flat and smooth surface. On the smooth surface of such carrier sheet there is applied a coating composition which on drying or setting-up results in the thin back size coating 28, and this composition is selected so that the back size coating adheres poorly to the surface of the carrier sheet, so as to permit of ultimate stripping apart, but is capable of firmly bonding to the next applied coating. There is next applied an aluminum pigmented coating composition which anchors to the back size coating and on setting-up provides the reflector film 2|. This in turn is coated with a colored transparent composition to provide the colored spacing film 22, over which is formed the transparent binder coating 23 in which the layer of small spheres 24 is partially embedded. Following completion of the reflector sheet, the carrier sheet 25 may be stripped oli as a step in the manufacturing operation. However, the carrier sheet may Ibe retained in place to serve as aliner and temporary support for the reflex reflector sheet proper, being removed by the user at the time of making up a sign (as indicated in Fig. 3). This carrier sheet when thus retained will not interfere with the ready cutting of the whole sheet, as during slitting operations in making up rolls or cutting of the sheet to desired sizes or shapes. The back size coating may be omitted and the reflector film cast directly on the surface of the carrier sheet when the reector coating composition is so chosen, with respect to the surface character of the carrier sheet, as to cause low adhesion of the reflector film which will allow of ultimate stripping ofi'. Illustrations of production methods are set forth in more detail hereinafter in Examples 1 and 2.

Fig. 4 shows a ready-to-lay type of backless colored reflex reflector sheet. Reference numerals 2|, 22, 23, 24 and 26 designate the identical backless reflector sheet shown in Fig. 3, the carrier sheet 25 having been stripped oil. An adhesive coating 21 is bonded to the back face of the reflector sheet; and, if desired, a temporary removable liner 28 may be applied to the exposed back face of the adhesive coating as a protection and to separatethe adhesive coating -from the surface of the layer of spheres if the sheeting is' wound in rolls. The adhesive should be waterproof for use in making outdoor markers or signs, and may be of a normally non-tacky kind, which is activated to a tacky state by use of a solvent, or heat, or both; or it may be a normally tacky (pressure-sensitive) type. The removable liner may be, for example, a sheet of straight (nonmoisture-proofed) Cellophane (regenerated cellulose film), which can be readily removed -by moistening with water and peeling olf.

Figs. 5 and 6 show a highway stop sign illustrating a use of the colored reflex reflector sheet of the backless type described in connection with Figs. 3 `and 4. The sign base is a regular embossed metal sheet 30, the lettering being raised above the background by embossing, as illustrated by the sectional View of a portion of a letter 3l shown in Fig. 6. Over the whole surface area of the base there is applied and bonded a stretchy backless reflex reflector sheet 32, having the type of structure previously described in connection. with Figs. 3 and 4; the removable carrier If a sheet is used then being applied thereover while the adhesive coating is still tacky. Conformation of the sheet to the surface can readily be made by pressing down the laminated sheet by means of a soft roller. If any air pockets are formed under the reflector sheet, or any buckles result, they can be removed by -locally pricking through or slitting the sheet and then Pressing down to provide smooth contact and conformation to the base surface. 'Ihe applied sheet can be originally cut to provide margins extending beyond the base area, which can be folded back around the sign edges, or can be trimmed oil! to provide accurate coverage. A preferred type of adhesive or cement is one of the polymerizing kind which set-ups by polymerizing after being applied. If applied in a solvent vehicle (used to facilitate coating) the sheet is applied after the solvent has evaporated from the adhesive coating in order to prevent the `solvent from being trapped. When a ready-tolay type of sheet is used, having an integral back coating of adhesive (as shown in Fig. 4), it can be applied directly, the adhesive being activated in any suitable way, before or after application of the sheet to the base, depending on the nature assasu the present invention. And in this connection it is of importance that the present invention provides a highly weatherproof reflex reector sheet This example illustrates a method of making colored reflex reflector sheeting of a nstretchy and The lettering will then appear black, as in the l ing 'a yellow dye or transparent pigment in the 'a 40 lb. per ream Acme Fourdrinier paper, or a 70 lb. Duracel Fmmirinier paper), by knife-coating one side with the following solution in an amount sumcient to provide a dried coating having a weight of about l0 grains per 2 4 sq. in. `Formula proportions are in parts by weight:

viny1 acetate polymer (such as ava'r type com by carbide s, carbon chemicals Corp.) Ground mica 17.5 Denatured ethyl alcohol 65 'I'he coating may he dried by heang at 12o-130 Y F. for half an hour, to evaporate the alcohol soltransparent spacing nlm. The background areaV diiluse daylight) and by night (when viewed by reflex reflection by occupants of approaching vehicles, the head lights providing the incident light and the occupants being near the axis so as to be within the brilliant cone of returning light) A further advantage of the "backless film type construction of the reex reiiector sheet, is that it resists vandalism. If a Yvandal attempts to pry or strip oil the reflector sheet from the base to which it is bonded, the nlm sheet will tear or break locally so that only a very small piece can be removed at a time, making the enterprise so difficult and protless as to discoin'age the eiiort. The present invention provides a way by which existing embossed trame signs can be readily and inexpensively converted to signs of the reilex type having a very billiant and live color which demands attention. The stretchy reflex renector sheeting can be applied to the metal sign base without the need of highly skilled labor or elaborate equipment, as is apparent from the foregoing description. This results in a large saving of cost in replacing conventional signs with signs of the reex reflecting type. and provides an added inducement to highway and traillc authorities to make the change on an extensive scale. The feasibility of highway safety devices depends not only on technical operativeness but on economic considerations, and hence this factor is of importance to the real usefulness to the public of vent. The coating adheres ienaciously to the paper and provides a smooth surface adapted to receive they reiiector iilm coating. This surface coating for the carrier web is chosen with reference to the composition of the reflector iilm coat'- ing so that when the latter is applied in solution form it will have a good wetting action and initial adhesion to the carrier web sm'face, but will adhere poorly on completion of drying or curing so sg'eiermit of shipping apart when subsequently The following reflector film coating composition may be used to secure the desired result, being applied over the coated face of the carrier web by knife-coating in amount which will produce an ultimate dried iilm weighing about i0 grainspex-Z! sq.in.:

Polyvinyl butyl-al (such as Wnylite XYSG sold by Carbide I: Carbon Chemicals Corp.) 16 Flaked aluminum pigment (such as aluminum lining powder) l2 'Ircresyl phosphate 8 Denatured ethyl alcohol 'I2 "rnereaector nim coating may be dried at 12o'- appearing to be reflective Parts Other polyvinyl aldehyde polymer resins can be used in place of the polyvinyl butyral to provide suitable stretchy films.

The transparent colored spacing film Vis next formed by knife-coating the reflector lm surface with the following composition in amount to produce a dried film of the desired thickness relative t the average diameter of the spheres to be used. Assuming the use of No. 11 beads having a diameter range of approximately to 6 mils, and that a spacing distance of approximately 2 mils is desired, a dried spacing lm weight of approximately 20-21 grains per 24 sq. in. is suitable, when formed from the following coating composition:

Polyvinyl I'butyral (such as Vinylite XYSG) 18 Tricresyl phosphate 9 Denatured ethyl alcohol 83 Soluble dye 0.3-3

The resultant spacing coating may be dried for half an hour at 1Z0-130 F. and provides the colored transparent spacing film. This lm is integrally bonded to the underlying reflector lm and is likewise waterproof, flexible and stretchy. It is sunfast and is not darkened nor deteriorated by the suns rays on outdoor exposure. The soluble dye should be soluble in the coating resin (in this case polyvinyl butyral) and should be of a light-fast type and insoluble in water. The following are examples of commercially available dyes which may be employed in the above formula: "Dupont Luxol Fast Blue MBS (made by E. I. du Pont de Nemours & Co.); and Azosol.

Fast Red BBA, Azosol Fast Yellow GRA and "S0163 Auramine D. C. Conc. (a yellow dye), made by General Dyestuff Corp. Mixtures of dyes of dierent color can of course be used to produce various shades of color. The intensity of color can be controlled by varying the proportion of dye.

An uncolored transparent bead binder coating is next applied by knife-coating the following coating composition over the spacing film, a wet weight of -13 grains per 24 sq. in. being s uitable for holding No. l1 beads or spheres of vapproximately 5 to 6 mils diameter:

Heavy blown castor oil 100 Beetle No. 227-8 (50% solids) 200 having a refractive index of about 1.53 and a diameter range of about 5 to 6 mils, are applied in excess to form the lenticular light-returning layer, the beads sinking down in the wet coating until they touch, or closely approach, the surface of the colored spacing lm. Positioning of the beads can be facilitated by passing the web over a batter. around a roller to cause excess beads to fall off.

The Web, with its applied coatings, is then festooned on racks and oven cured to set-up the bead binder coating, using a curing time of 50-60 minutes at 212 F. Any surplus beads adhering to the surface can be removed by passing the web 'I'he web may then be passed downv around a roller and subjecting the beaded surface to the action of a rotary brush and air blast, or by employing a knife blade spaced just far enough to catch and remove excess beads projecting above the proper layer of beads. The reflex reflector sheet'can then be stripped from the coated paper carrier web and the latter can bereused.

The resultant colored backless reflex reflector sheet will stand extensive outdoor exposure without substantial deterioration or loss of eilciecy. It is quite flexible or pliant and is well adapted to application over the surfaces of embossed sign bases, having a dead-stretch and a high degree of stretchiness. The sheet` may be readily lcut into pieces or desired shape and size. It can -be cut by hand, using a knife or shears, or can be cut mechanically. The glass spheres or fbeads are rmly bonded and do not loosen and fall out when the sheet is stretched. The following data shows the mechanical 'properties in a quantitative way, being based on sheets made as described in this example, using No. 11 glass beads (5 to 6 mils diameter). f

The backless sheet (after removal of the 'carrier web) had a total caliper thickness of approximately 13 mils, as measured by a machinists micrometer. This represents the maximum thickness, between the back face and the outer extremities of the beads which project farthest,` rather than the-average thickness as might be calculated from the average bead diameter and thickness of the spacing and reflector hns (such average thickness -being somewhat under -10 mils). The sheet had a tensile strength of approximately 10 lbs.v per inch width and a stretch of 110%.

The strength and stretch values were measured on a regular Model 3'7-4 electro-hydraulic tensile tester, made by the Thwing-Albert Instrument Company, of Philadelphia, Pa. The jaw opening was 4 inches, the initial length of the test strip subjected to tension thus being 4 inches, and the machine was set to produce jaw separation at the rate of 15 inches per minute. The test strips were cut to an accurate width of one-,half inch, and

' hence the tension value in pounds is lmultiplied by two to give the tension per inch of width. The machine indicates the tension force and the extent of elongation of the test strip at the time of rupture. A stretch of 110% means that the 4 inch initial length of the strip (between jaws) had increased to 8.4 inches when rupture took place l(i. e. the stretch is the increment of length divided by the original length, multiplied by 100 to give the percentagey value). The tensile strength is the'tension force exerted just prior An alternative procedure which may be emthe aluminum fiake reflector nlm prior to applying the transparent spacing lm. The web, with the reflector coating formed thereon, may be readily printed on a rotary multi-color offset press, using transparent colored inks to form the lettering. designs, symbols, etc., and the background areas. The inks may have the formulation previously described for the colored transparent spacing film composition, appropriate dyes being used to obtain a variety of colors. The proportion of dye should be greater since the thickness of the printed coatings will be much less than the thickness of the spacing film. Following drying of the printing, theremaining procedure 4is the same as previously described except that the dye is omitted from the spacing film coating composition. The latter-may be applied in a slightly The lower coating weight if the thickness of the printing is. appreciable. 4The result in the product is that the transparent printings-produce a colored sign having the re'ex reecting properties that have been indicated.

'ExAMgLa 2 This example illustrates a variation in making technique and the use of transparent pigments for coloring the spacing nlm. The same general procedure described inthe preceding Example 1 is used, except for the provision cfa back size coating to provide a back surface which will adhere poorly tothe particular carrier web employed so as to permit ready stripping without moistening (the structure being'that shown in Fig. 3). Y Y

paper carrier web is surface coated with a 40% solutionof isobutyl methacrylate polymer in xylol, using a coating weight (web) -of 13-16 `grainsper 24 sq. in., and is dried for l5 minutes at 120 F. to evaporate the xylol. This provides the smooth casting surface, adapted to permit ready stripping of the reflector sheet. A back size coating is then applied to the casting surface, using a 10% solution of polyvinyl butyral (such as Vinylite XYNC sold by Carbide 8: Carbon Chemicals Corp.) in Ethylv Cellosolve (ethylenegUcol monethylether), applied with a wet weight of 20 grains per 24 sq. in., followed by oven drying for one hour at 140 C. This back size coating bonds to the next applied reflector coating, but adheres poorly to the casting surface.

The reflector coating composition is comprised of 100 parts of an oil-modified air-drying Phenolic resin base varnish, containing 10 parts of aluminum flakes (such as aluminum lining powder),

Beetle No. 227-8 (50% solids) 100 Heavy blown castor oil 50 Transparent pigment 0.5-2

The lm is cured for one hour at 200 F. iThe transparent pigment should be light-fast and have a refractive index approximately equal to that of the cured resin lm 'so as not to cause appreciable scattering of light and loss of transparency. The use of transparent pigments' in printing inks is well known and many suitable pigments are available on the market. The following are examples which have proved quite satisfactory in the above formulation:

Lake pigments, such as, for example, Dupont Yellow Lake YP440Dl and Dupont Alizarine Red Lake RT-332-D.

Phthalocyanine pigments,` toners and lakes; which are distinguished from phthalocyanine dyes by lack of solubility and each of which serves as a colored pigment. This class of coloring agents is described in an article in Industrial and Engineering Chemistry, July, 1939, pages 839-847. Examples `are the Monastral colors sold by E. I. du Pont de Nemours & Co., such as Monastral Fast Blue GS, Monastral Fast Green GS and Monastral Blue Toner BT172-D.

In making up the colored coating composition, the preferred procedure is to prepare a concentrate by milling together the pigment and suilicient of the castor oil resin mixture to provide about 8.20% byweight concentration of the pigment, relative to the solids content. In calculating the percentage of pigment, the solids content of the castor oil and resin mixture is equal to the weight of castor oil plus one-half the weight of the Beetle No. 227-8" (since the latter is half resin and half solvent). This concentrate is then blended for use with a sufllcient further amount of the mixture of castor oil and Rezyl No. 227-8 to bring the pigment percentage down to the desired value. For making a transparent colored spacing i'ilm as set forth in the foregoing description, the percentage of pigment will ordinarily be about 0.52.0%, the proportionbeing adjusted to give the desired color intensity. The ultimate color intensity depends on'the thickness of the colored film or coating. Thus a coating or film made half as thick would need double the percentage oi' pigment to produce the same effect.

The transparent -bead binder coating is next applied, and has the same composition yas the above spacing lm compositionexcept that the pigment is omitted. A layer of No. ll glass beads is embedded therein and the coating is then cured for one hour at 200 F. I

'I'he resultant backless" colored reflex reflector sheet can be readily dry stripped from the carrier web and the latter can be reused. Ihis colored reflector sheet is quite pliant and is highly waterpoof and proof against delamination, and is suillciently stretchy to permit of ready conformation to the surfaces of embossed sign bases.

An alternative procedure is to cast the transparent colored spacing 111m directly on the coated carrier web (omitting the back sizing coating and reflector coating), followed by application of the binder coating and glass bead layer. The resultant colored transparent beaded sheet can be readily stripped from the carrier web and can be laminated to any desired base or sheet having a silvery metallic reflecting surface, to make a reector sheet or sign. Thus it may be laminated to an aluminum foil or to a sti sheet of alumisuch portions, as for example to provide black l letteringl visible by contrast to. the surrounding reflective background which will appear colored in the product. The beaded sheet can be readily laminated to foil by application of heat and pressure. It can also be readily laminated to the reflector surface by using a thin interposed transparent coating of liquid adhesive comprised of 100 parts Beetle No. 227 and 50 parts of heavy blown castor oil, which is subsequently cured by heating.

The preformed transparent colored beaded film can also be coated, painted or printed on its back face with an aluminum flake reflector coating, or can be given a plating of silver, for example.

EXAMPLE 3 This example illustrates the making of a transparent stretchy beaded sheet which is uncolored and which can then be used in various ways in making reflectors and signs in accordance with this invention.

The same type of carrier web is employed as in the preceding Example 2, surfaced with a coating assasss weights: approximately so grains per 24 sq. m. with the following formulation: Beetle No. 227-8" 5o% sends) 10o Heavy blown castor oil. 50

is stripped from the carrier web. This may be l employed as a stock sheet for vmaking reilectors and signs of various types and colors, as indicated by the following illustrations.

One general procedure is to apply a thin transparent colored coating or coatings to the back face oi.' the beaded sheet to provide the desired color eil'ect; and then to laminate the sheet to a base sheet having a silvery metallic reflective surface, thereby producing a colored reflector or sign. The colored coating composition can be applied in any suitable way, by hand or machine. Thus it may be readily applied by using an oflset printing press. By using multi-color oiIset printing methods, so that different color coatings are applied in different areas, it is possible to readily prepare multi-color signs in large numbers. Signs can also be made by using the silk-screen method for applying different color coatings to dill'erent` areas to form the lettering, designs, symbols, backgrounds, etc., of contrastingcolor.

Hand

painting can be used where only a single sign,

or a few signs, are to be made.

A second generalprocedure is to coat, print or paint the "silvery metallic reilecting surface of a base or sheet (such as aluminum foil), using transparent colored coating compositions, to provide the desired color eiect; and then to laminate the transparent beaded sheet to the surface, thereby producing a colored reilex reilecting rerlector or sign.

In either case, the result is a laminated structure in which is embodied the principle oi the present invention, since the layer oi' transparent spheres is spaced from an underlying silvery metallic reilecting surface and there is an interposed transparent fllm or stratum which is colored, so as to cause colored reilex reilection oi' outstanding brilliancy and liveness. The colored coating can be omitted from one or more areas so g as to result in an uncolored transparent aperture signs in which the entire area has a transparent color illm underlying the layer oi spheres.

Suitable transparent colored coating compositions for use as described above, can-be` made by using the resin and castor oilrblend previously described for use in making the beaded sheet. This resin and castor oil composition can be colored by grinding in 5 to 20% by weight of the` desired colored transparent pigment. The viscosity canjze reduced by thinning with a solvent, such as normal butyl Cellosolve (normal ethyleneglycol monobutylether), in order to increase the ease of applying, depending on the method employed. 'I'he concentration of pigment should 9 behisnertnmmnximpleasossmobnmtne 'desired intensity oi' color in a coating relatively glue? thinnerthan the spacing nlm oi' the beaded After printing, screen processing, painting or otherwise color the transparent beaded sheet, or the reilective base o'r sheet, depending on the type of procedure used, the beaded transparent sheet is laminated to the reilective base or sheet to provide the desired reilector or sign product. This can be done by simple hotpresslng, due to the thermo-adhesive properties of 4the castor oil resin coating. The setting-up of the castor oil resin. coatings can be combined in the same operation. being completed by the hot pressing laminating operation. If desired a, `thin interposed laminating adhesive can be applied, using the transparent castor oil resin composition (without color), iollowed'by pressingto insure intimate contact of the lamina and heating 'Y to set-up the transparent adhesive coating. This results in a strong and waterproof bonding.

The following examples illustrate variations of the foregoing example wherein a preformed,

transparent spacing nlm is employed in making the transparent beaded sheet, which can then be coated on its back face with transparent color coatings, before lamination to the reilective base or sheet, or can be laminated directly to a refiecf tive base or sheet which has been coated on its face with transparent color coatings.

chloride (such as Plioiilm) is coated on one side with the necessary thickness or a bead binder,

composition comprised of 100 parts oi heavy blown castor oil and 200 parts oi Beetle No. 227 the layer of glass beads is applied and the coating is cured by heating at 212 F. for 50-60 minutes.` The application of this binder coat, as described, results in a nal sheet which is even stretchier than the original "Pliolm sheeting, Colored coatings of the kind described in the preceding example can be employed in connection with the technique described. Du'eto the highly stretchy nature of this Plioillm" beaded sheet, it will generally' be more convenient to color coat the reflective base or sheet vand then laminate the beaded v"Plioiilm" sheet thereto. The thermo-adhesive nature of the Plioillm assists in making'tor strong bonding.

, It is also possible to `employ a transparent "Pliotilm" sheeting which is itself colored (by incorporation of a suitable dye or transparent pigment during its manufacture), resulting in a colored transparent beaded sheet which can be readi1y laminated to e renective base or sheet to make a colored reilex reector. The thermo-adhesive property of the "Pliolm nation by hot pressing.

Other examples of transparent stretchy iilms are illms of polyvinylidene chloride ("Saran), plasticized polyvinyl chloride (Koroseal"), and plasticized polyvinyl butyral.

Exnlru. A A web of cellulose acetate lin is coated with a The "Rezyi No. 5'3" (made by American cyanemid l: Chemical Corp.) is a two-component liquid permits of readylamibead binder composition comprised oi' a, mixture n aixyd resin 'of the :menne-hunne anhydride After application of the glass bead layer. the

sheeting is oven heated for 30 hours at 165175 l". to dry and cure the binder coating.

The same alkyd resin binder composition mayv be used as a base in which suitable dyes or transparent pigments may be incorporated for providing transparent color coating compositions for use in making reflector' or sign products in the,

, moval following pplicaticnof the glass beads,

which maybe accomplished by festooning the coated web `racks and passing through an oven at 150 F. for 1 hour. Y

Adhesive back coatings yA wide varietyfof adhesives are suitable for coating on the back face'of "backless" reflex reilector sheets, as herein describedl (as in Examples .1 and 2), to provide a sheet of the ready-to-lay type (such as is illustrated in Fig. 4, for example) An example of a rubber-resin pressure-sensitive adhesive is one compounded of rubber and a taclrlfler, such as rosin or ester gum in lesser proportion than the=rubber, and which may include a reinforcing pigment such as zinc oxide, being dissolved in heptaneivolatile solvent) to provide a coatable viscosity. An adhesive of this type is described in R. G. Drew Patent No. 2,236,527, issued April 1, 1941.

A further example is .a pressure-sensitive adhesive compounded of polyisobutylene ("Vistanex) and a lesser proportion of tackifler resin (suchcas hydrogenated indene resin) as described in H. J.l Tierney Patent No. 2,319,959, issued May 25, '1943, which lists numerous suitable rubbery base and tackiiler materials.

The adhesive solution may be coated on a Cellophane liner sheet, followed by drying to evapcrate oi the volatile solvent vehicle, and is then laminated to the back face of the reflector sheet, as by passingthe two sheetsbetween squeeze rolls with the tacky adhesive surface contacting the back face of the reector sheet. The Cellophane liner may be left in place' (as shown in Fig. 4) to be removed when desired by meistening and peeling on; or it may be removed following, lamination and the reector sheet may be wound directly in a roll without using a liner, subsequent unwinding being facilitated by the limited area of contact between the extremities of the beads and the contacting adhesive coatins.

Pressure-sensitive .adhesive coatings as described above, while taclqr, are eucohesive," by

, which it is meant that they are more cohesive than adhesive such that offsetting or transfer ofA adhesive material does not result when a sheet or tape coated therewith ris unwound from rolls or removed from surfaces to which temporarily applied, and can be handled without transfer of adhesive material `to the ngers. 'I'hese adhesive coatings are waterproof, and are quite stretchy and hence suitable for use in making stretchy sheet material.

The following is an example of an adhesive coating solution which may be applied to provide (after evaporation ofthe solvent vehicle) a waterproof and stretohable adhesive coating which is both solvent-activatable and heat-activatable:

. Parts Rubber base 102 45% reclaim rubber 45% zinc oxide combined on rubber mill 10% latex crepe.` r Rosin 29 Nevillife Resin of C. melting point (hydrogenated indene-coumarone resin) 21 Oleum spirits (volatile petroleum hydrocarbon solvent of 306-424 F. boiling range) 80 Ethyl alcohol (denatured with gasoline) 1 The components are mixed in an internal mixer (such as Mogul) until a homogeneous solution .is obtained. The ethyl alcohol serves as a viscosity-reducer and may be omitted by using a Alarger proportion pf the solvent.

The adhesive solution isy coated upon the back `surface of the beaded sheeting, as by use of a time a liner of regenerated cellulose film (Cel lophane) is wound in so as to contact the adhesive surface and be detachably adhered thereto, thereby covering the adhesive surface to prevent sticking of the adjacent beaded surface and to facilitate use of the sheeting.

Alternatively, the adhesive coating can be applied by a transfer method as has been described in connection with pressure-sensitive adhesive coatings. In this case the adhesive coated Cellophane liner is laminated to the back surface of the beaded reflector sheeting before the adhesive coating thereon has been fully dried (i. e. while still slightly tacky and warm). the trace of residual solvent being left in.

The Cellophane liner can be removed, after the sheet is cut to shape in making up signs, or whenever desired, by moistening with water and peeling off.

The adhesive coating may be activated to a tacky surface condition by moistening with V. M. P. naphtha, heptane or gasoline, etc. The sheet is then applied to the sign base and is held by the tacky adhesive during setting of the adhesive as the result of solvent evaporation. Or the refictor sheet may be applied directly to the base and activated by heating with an iron or by placing in an oven (at say 225 F. for ilve minutes), followed by rolling to produce firm contacting.

Having described various embodiments of my invention, for purposes of illustration rather than limitation, whatl I claim is as follows:

1. A colored reex light reector comprising a light-returning layer of small uncoloredl transparent spheres held in position by a binder, an underlying reflector having a silvery metallic reiiective surface spaced from the inner extremities of said spheres, and an interposed transparent spacing layer at least part of which constitutes a colored transparent stratum serving as a light lter between the layer ofspheres and the reflective surface.

2. A colored reflex light reflector according to claim 1. wherein the reilector is a metal film having a silvery reective surface.

3. A colored reflex light reflector according to Y y 2,888,884 claim l, wherein the reflector is a stiff metal sheet having a silvery reflective surface.

4. A colored reflex light reflector according to claim 1, wherein the reflector is a film containing aluminum flakes lying approximately flat at the surface and providing av silvery semi-specular reflective surface.

5. A colored ieex light reflector comprising a reflector having a silvery metallic reflective surface, an overlying colored transparent spacing film, a light-returning layer of small uncolored transparent spheres overlying said spacing film and a binder coating holding said spheres in fixed position. y

6. A colored reex light reflector according to claimv 5, wherein the colored transparent spacing film contains transparent color pigment particles.

7. A colored reflex light reflector comprising a reflector having a silvery metallic reflective surface, a thin transparent colored coating bonded to said reflective surface, an overlying uncolored transparent spacing film bonded to said colored coating, and an overlying light-returning layer of small uncolored transparent spheres bonded to said spacing lm.

8. In combination with a silvery metallic reflective surface and laminated thereto, a self-sustaining preformed uncolored transparent exible beaded sheet for producing reflex reflection, having a flat back surface and a light-returning layer of small transparent spheres spaced therefrom, and a thin transparent colored coating interposed between said back surface of the beaded sheet and said reflective surface.

9. A exible colored reflex light reflector sheet adapted to be made in roll form and to be readily cut into pieces in making markers and signs, comprosing a flexible reflector sheet having a silvery metallic reflective surface, an overlying flexible transparent spacing layer at least part of which constitutes a colored transparent stratum, and

an overlying light-returning-layer of small yglass l num flakes bonded to the back side of said transparent sheet, there being no permanent or integral backing underlying the reflector lm, and said transparent film including a transparent colored stratum constituting a color filter between the layer of spheres and the reflector film; the

product constituting a thin and pliable, unitary,

colored reflex reflector sheet adapted to be readily cut and to be readily attached to base surfaces in making markers and signs.

11. A backless" colored reflex reflector sheet according to claim 10, further characterized by being stretchy to the extent o1' at least about 20% l as herein described.

PHILIP V. PALMQTQJIST. 

